Method for producing methanol

ABSTRACT

A graded temperature methanol reactor includes an inclined container containing a liquid heat transfer medium, such as water, having a varying temperature along the container. Conduits, extending through the container and in contact with heat transfer medium, conduct a feed gas having hydrogen and carbon monoxide and permit heat transfer between the feed gas and the heat transfer medium. A copper catalyst is disposed within each conduit to cause the hydrogen and carbon monoxide to react to form methanol, which condenses as the temperature decreases along the container from the upper end to the lower end. Preferably, the conduits are configured as a rotor and can be rotated relative to the container. By using this methanol reactor, methanol can be produced from a feed gas having hydrogen and carbon monoxide in a 2:1 molecular ratio, regardless of the source of this feed gas. For example, this feed gas can be produced by a biomass gasification and reforming process, and the methanol reactor can be interrelated with the gasification process.

This application is a division of application Ser. No. 08/349,912, filedDec. 6, 1994, (status: pending).

FIELD OF THE INVENTION

This invention relates to a reactor and process for producing methanolfrom a feed gas having hydrogen and carbon monoxide in an approximate2:1 molecular ratio. In addition, the present invention is directed to aprocess for producing methanol from a feed of a biomass containingcarbon, hydrogen and oxygen.

BACKGROUND OF THE INVENTION

Methanol synthesis is the simple addition of hydrogen to carbonmonoxide. This reaction is reversible, with the position of equilibriumdetermined by pressure, temperature, and concentration as follows:##STR1## The reaction rate of approach to equilibrium is a function oftemperature alone. More particularly, as temperature increases, thereaction rate increases.

Two known commercial processes for producing methanol use uniformtemperature reactors. In the first known process, hydrogen and carbonmonoxide are fed to a reactor having an "optimum" temperature. Anoptimum temperature is sufficiently low to drive the above methanolsynthesis reaction towards methanol without significantly compromisingthe rate of reaction. Then, the reactor is quenched in order to condensethe methanol so that it can then be separated. After methanolseparation, the reactor is again heated up for the next cycle.

The second known uniform-temperature methanol reactor involves passingthe reactants through a boiling water reactor. Then, the exit gas fromthe reactor is fed to a condenser where the methanol can be separated.Subsequently, the gas is rewarmed and recycled, with the addition offresh synthesis gas to prevent the buildup of impurities.

In each of these two known processes, the reaction is driven graduallytowards completion, with only about a ten to twenty percent degree ofreaction with each stage. In addition, each process requires the step ofpurging a certain amount of the stripped gas during each cycle, in orderto prevent a significant build-up of methane and trace inerts, such asnitrogen.

SUMMARY OF THE INVENTION

The present invention relates to a graded temperature methanol reactor,which includes an inclined container containing a liquid heat transfermedium, such as water, having a varying temperature along the length ofthe container. The container has an inlet opening near its lower end topermit the heat transfer medium to enter the container, and an outletopening near its upper end to permit the heated heat transfer medium toexit the container as a vapor. The reactor also includes conduitsextending within the container and in contact with the heat transfermedium. The conduits conduct a feed gas having hydrogen and carbonmonoxide in an approximate 2:1 molecular ratio and permit heat transferbetween the feed gas and the heat transfer medium. A copper catalyst isdisposed within each conduit to cause the hydrogen and carbon monoxideto react to form methanol, which condenses as the temperature decreasesalong the container from the upper end to the lower end.

According to another embodiment of the present invention, the conduitsare configured as a rotor which is disposed coaxially within thecontainer. According to this embodiment of the present invention, adevice, such as a drive motor along with a drive gear, rotates the rotorrelative to the container. Also, the rotor includes a first bored stubshaft extending through the top end plate of the container to define anintake bore for conducting feed gas to the conduits. The rotor includesa second bored stub shaft extending through the bottom end plate of thecontainer.

The present invention also includes a process for producing methanolfrom a feed gas having hydrogen and carbon monoxide in an approximate2:1 molecular ratio. The process includes first compressing and heatingthe feed gas, preferably to a pressure of about 1,400 psi to 1600 psiand to a temperature of about 550° F. to 650° F. After a heat transfermedium is introduced the interior of an inclined vessel, the feed gas isintroduced into the conduits extending through the interior of thevessel. The feed gas is exposed to a copper catalyst which is disposedin the conduits to cause the hydrogen and carbon monoxide to react toform methanol which condenses along the vessel causing further formationof methanol. According to another embodiment of the process of thepresent invention, the process includes rotating the conduits within thevessel.

The present invention also includes a process for producing methanolfrom biomass. The process according to this embodiment includes addingwater and an alkaline catalyst to the biomass feed to form a feedmixture, which is charged into an interior chamber of an inclined rotorkiln. The feed mixture is heated to a temperature of from about 1050° F.to 1150° F. to produce a first gas mixture including hydrogen and carbonmonoxide. After traveling through the chamber of the rotor kiln, the gasmixture is heated in a gas reformer while being exposed to a nickelcatalyst to form a reformed gas mixture having a hydrogen and carbonmonoxide in an approximate 2:1 molecular ratio. Then, the reformed gasmixture is conducted through pipes which extend along the rotor kilnthrough its interior chamber. After condensing the mixture, impuritiesare removed and then the mixture is compressed and heated to about 1400psi to 1600 psi and a temperature of from about 550° F. and 650° F.Then, this feed gas is introduced into the conduits extending throughthe interior of the methanol reactor according to the present invention.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary, but not restrictive,of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is best understood from the following detailed descriptionwhen read in connection with the accompanying drawings, in which:

FIG. 1 is a partial longitudinal view of a methanol reactor according tothe present invention;

FIG. 2 is an enlarged longitudinal view of a conduit of the methanolreactor shown in FIG. 1; and

FIG. 3 is a schematic diagram showing a process for producing methanolaccording to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 shows an inclined container 10 which is configured as acylindrical pressure vessel. Container 10 contains a liquid heattransfer medium 12, such as water, which has a varying temperature alongthe length of the container. More particularly, the liquid heat transfermedium 12 is introduced into container 10 through inlet opening 14 as acooled liquid. The heat transfer medium exits container 10 as a vaporthrough an outlet conduit 16 (defining an outlet opening) near the upperend of the container.

Disposed within outlet conduit 16 is a valve 74, which is configured toplace the heat transfer medium under pressure such that most of the heattransfer medium exists as a liquid in the container 10. For example, ifthe gas entering the container 10 has a temperature of about 600° F.,and water is used as the heat transfer medium, valve 74 would beconfigured to keep the pressure of the heat transfer medium in thecontainer 10 at about 700 psi.

According to one embodiment of the invention, the liquid heat transfermedium is water and is introduced through inlet opening 14 at atemperature of about 100° F. and exits outlet conduit 16 as a vapor at atemperature of about 550° F. The temperature of the water graduallyincreases from the lower end to the upper end of container 10. As thetemperature of the water increases, it becomes less dense so that itprogresses toward the upper end of container 10. Any other suitable heattransfer medium may be used, so long as the heat transfer medium becomesless dense with increased temperature.

Container 10 includes an outer cylindrical surface 18, a top end plate20 at the upper end of container 10 and a bottom end plate 22 at thelower end of container 10. As shown in FIG. 1, container 10 is inclinedslightly. According to one embodiment of the invention, the reactor isdisposed at an angle of about 15° from horizontal, although the angle ofinclination can vary significantly depending on process conditions.

As shown in FIG. 1, a plurality of conduits are disposed withincontainer 10 and are in contact with heat transfer medium 12. Conduits24 conduct a feed gas having hydrogen and carbon monoxide in anapproximate 2:1 molecular ratio along their length from the upper end tothe lower end of container 10. In addition, conduits 24 permit heattransfer between the feed gas and the heat transfer medium.

Each of the conduits 24 (or pipes) are in fluid communication with anintake bore 26 defined by a first bored stub shaft 28 which extendsthrough top end plate 20. Seals 30, such as known stuffing boxes, aredisposed between first bored stub shaft 28 and top end plate 20. Each ofthe conduits 24 are also in fluid communication with an exhaust bore 32defined by a second bored stub shaft 34 which extends through bottom endplate 22. Once again, seals 30, such as stuffing boxes, are disposedbetween second bored stub shaft 34 and bottom end plate 22.

A copper catalyst is disposed within each of the conduits 24. The coppercatalyst, which causes the hydrogen and carbon monoxide to react to formmethanol, may be disposed within conduits 24 in any known manner, suchas by adhering the copper catalyst to the inside of conduits 24, or byplacing the copper catalyst within a screen disposed within each conduit24. Alternatively, as shown in FIG. 2 which is an enlarged view of aconduit 24, a chain 35 may be disposed within each conduit 24 and thecopper catalyst may be disposed as pellets 36 within the links of thechain 35.

As shown in FIG. 1, a double-plate intake manifold 40 is disposedbetween first bored stub shaft 28 and conduits 24. Intake manifold 40includes a first plate 42 closer to the upper end and having a secondplate 44 closer to the bottom end and spaced from first plate 42 to forman intake manifold interior. Each plate 42, 44 includes a plurality ofholes through which the conduits individually extend.

Similarly, a double-plate exhaust manifold 50 includes a first plate 52closer to the lower end of container 10 and a second plate 54 closer tothe upper end of container 10 and spaced from first plate 52 to form anexhaust manifold interior. Each plate 52, 54 has a plurality of holesthrough which conduits 24 individually extend. Conduits 24 have boresnear their ends to permit communication between the interior of conduits24 and the intake manifold interior, and the interior of conduits 24 andthe exhaust manifold interior. The intake and exhaust manifold aresimilar to that shown in FIG. 5 of applicant's co-pending applicationentitled APPARATUS FOR PRODUCING METHANE-RICH GAS USING A FIXED KILNWITH ROTOR STEAM GASIFIER, filed on the same day as this application andincorporated herein by reference.

Covers individually engage each of the conduits 24 at the ends of theconduits. In addition, swivel connections may be individually mounted tothe covers and individually connect the chains to the covers forpermitting relative rotation between the chains and the covers as theconduits 24 rotate.

According to an embodiment of the present invention, the conduits 24 areconfigured as a rotor. According to this embodiment, a drive gear 70 isdriven by a motor 72. Gear 70 is coupled to either first bored stubshaft 28 or second bored stub shaft 34 and causes the stub shaft torotate. Because the conduits 24 are connected to the stub shafts, theconduits also rotate along with the stub shaft. Thus, conduits 24 aredisposed as a rotor coaxially with container 10.

According to this embodiment, the catalyst is preferably selected aspellets 36 and chains are used to maintain the catalyst pellets 36 inposition. Accordingly, when the conduits 24 rotate, the copper catalystpellets 36 are slightly abraded by being contacted against the chainlinks and the interior of the conduits 24. This causes the coppercatalyst to stay fresh longer. Another advantage of configuring theconduits 24 as a rotor is improved heat transfer. Movement of theconduits 24 through the water (e.g., at about 1-2 rpm) will aid heattransfer from the conduits 24 to the heat transfer medium. Also, thechains and pellets will cause gentle gas turbulence within the pipes,and their movement with rotation will aid in the heat transfer from gasto the conduits 24.

Also, the reactor may include at least one spider plate 76 which ismounted to the exterior of the conduits 24. The spider plates 76 serveto stabilize conduits 24. Also, the spider plates 76 have bores 78 forpermitting flow of the heat transfer medium.

The system also includes a separating vessel 80, which is in fluidcommunication with exhaust bore 32. The separating vessel serves toseparate liquid methanol from the purge gas.

The process according to the present invention includes compressing andheating a feed gas having hydrogen and carbon monoxide in an approximate2:1 molecular ratio. Preferably, the feed gas is compressed until apressure of 1400 psi to 1600 psi is achieved and is heated until thetemperature of the feed gas is from about 550° F. to 650° F. Even morepreferably, the feed gas is compressed until a pressure of 1500 psi isachieved and is heated until a temperature of 600° F. is achieved. Thefeed gas is then introduced into the plurality of conduits 24 throughintake bore 26 of first bored stub shaft 28. The heat of the gas istransferred to the heat transfer medium in the interior of container 10.

Upon exposure to a copper catalyst, hydrogen and carbon monoxide reactto form methanol in each conduit 24. As the reacting gases traveldownward through conduits 24, the temperature decreases gradually whichcauses further formation of methanol from hydrogen and carbon monoxide.Then, at a low enough temperature, for example of about 400° F. at 1495psi, the methanol begins to condense which drives the equilibriumreaction of methanol further to the right in the gaseous phase due tothe decrease in methanol concentration in the gaseous phase. Thisreaction is continued until the temperature of the gas drops to a rangeof from about 70° F. to 130° F., and preferably about 100° F. With thisprocess, a reaction yield of approximately 70% is attained.

The process may also include placing a chain 35 in each of the pluralityof conduits and placing copper catalysts as pellets 36 in the links ofthe chains thereby exposing the gas to the copper catalyst pellets 36 asthe gas is conducted through the conduits 24. In addition, the processmay include separating unreacted feed gas from the methanol product.Furthermore, the process may include filtering the methanol product toremove particulates formed by catalyst shedding. The process may alsoinclude rotating the conduits, preferably at a speed of about 1 to 2rpm.

The process of the present invention also includes a process forproducing methanol from a biomass feed containing carbon, hydrogen andoxygen. According to this process, the biomass feed is first gasified byusing a fixed kiln with rotor steam gasifier as disclosed in U.S. Pat.No. 4,597,772, which is incorporated herein by reference, or by thegasifier disclosed in applicant's co-pending application entitledAPPARATUS FOR PRODUCING METHANE-RICH GAS USING A FIXED KILN WITH ROTORSTEAM GASIFIER, filed on the same day as this application and alsoincorporated herein by reference. The gas produced by the gasifierprocess of either of these references is reformed, gives its heat to thegasification process, is purified, compressed and heated, then fed to amethanol reactor according to the present invention. FIG. 3 shows ablock diagram of the interrelation between the gasifier process of oneof the two references and the methanol reactor of the present invention.

The first step of the process is to add water and an alkaline catalyst,such as potassium carbonate or sodium carbonate, to the biomass feed toform a feed mixture. The term biomass is defined in the '772 patent, andmight include wood chips or corn stalks and about fifty percent water.Stages 81 through 83 of FIG. 3 represent the standard stages of thegasification process as the feed travels through the body of the kiln.During stage 81, moisture is evaporated as the temperature increasesfrom 100° F. to 500° F. During stage 82, the reactants are pyrolyzedinto gas, liquids, and char, as the temperature increases from 350° F.to 800° F. Finally, in stage 83, char and liquids are gasified by steamas the temperature increases to 1100° F. As shown in the '772 patent,the rotor kiln is tilted to permit gravity-driven travel in a firstdirection and includes a plurality of pipes extending along the rotorkiln, wherein each of the pipes defines a pipe flowpath isolated fromthe interior chamber of the kiln. During stages 81 through 83, the feedmixture is gradually heated to a temperature of about 1050° F. to 1150°F. to produce a gas mixture including CH₄, H₂, CO, CO₂, H₂ O, a traceamount of H₂ S, and about 1-2% condensable organic compounds.

The gas flows from the gasifier to a reformer 84, where it is heated inthe presence of a nickel catalyst from 1100° to 1500° F. The smallamount of liquid and tar in the gas as it enters the reformer cracksalong with the methane. Traces of H₂ S similarly are not harmful; nickelis not easily poisoned at these high temperatures in the presence ofsteam (based on an equilibrium analysis). The reformer 84 causes themolar gas composition to change as follows:

    ______________________________________                1100° F.                       1500° F.    ______________________________________    CH.sub.4      20%      3.8%    H.sub.2       12       39.2    CO            4        19.2    CO.sub.2      22       12.3    H.sub.2 O     42       25.4    ______________________________________

Most of the methane has been steam-reformed to H₂ and CO, and some ofthe CO₂ has been reduced to CO. Also, the ratio between H₂ and CO is now2.04 to 1.00, just right for methanol synthesis. This gas compositionshift is strongly endothermic, and the heat of reaction is supplied byburning part of the purge gas from the methanol reactor, as shown inFIG. 3.

The hot reformed gas gives a little of its heat to the incoming gas, andthen flows from the reformer 84 into the returning gas pipes 85 of thegasifier, with significantly more enthalpy than when it emerged from thekiln. The reformed gas will easily support the gasification process inregenerative mode. There are chains and pellets in the gas pipes, butunlike the usual gasification system, the pellets are inert ceramic,placed in the pipes just for turbulence and heat transfer, and the gasdoes not change in composition in its passage from the hot to the coolend of the kiln.

As the temperature decreases in the returning gas pipes from 1300° F. to300° F., some of the steam will condense in the pipes near the cool end,and give its head of condensation to the warming of the incomingfeedstock within the kiln. A condenser 86 completes the condensation asthe temperature is decreased to 70° F. Then, the gas is stripped oftraces of H₂ S and all but about two percent of CO₂ (needed to keep themethanol catalyst at the right degree of oxidation) in a known CO₂separator. For example, CO₂ separator 87 might represent a CO₂absorption vessel and a CO₂ release vessel which makes use of theBenfield process, which employs the following reversible reaction:##STR2## At this point, the molar gas composition of the gas isapproximately as follows: 5.9% CH₄, 61.8% H₂, 30.3% CO, and 2.0% CO₂.Then, the gas is compressed adiabatically in a compressor 88 and fedinto the methanol reactor.

As mentioned above, a quantity of the unreacted feed gas (i.e, purgegas) is conducted to the gas reformer 84 where it is burned for heatingthe gas fed to the gas reformer 84 from the kiln. The quantity of purgegas delivered to the gas reformer 84 should be sufficient for heatingthe gas mixture to about 1500° F. The remaining purge gas is recycled tothe interior chamber of the rotor kiln through the biomass feed system.

According to a preferred embodiment of the invention, steam from themethanol reactor, which is formed by the transfer of heat from the feedgas, is conducted to a steam superheater 90 atop the gas reformer toform superheated steam. This superheated steam may then be conducted toa steam turbine-generator 89 for generating power. The steam which hasimparted some of its energy to the steam turbine-generator 89 may thenbe conducted to the CO₂ separator 87 for transferring its heat ofcondensation to form water, which may subsequently be returned to themethanol reactor 10.

Typically, the step of gradually heating the feed mixture as itprogresses throughout the kiln, as shown in blocks 81 through 83, lastsfor about 30 to 90 minutes. Initially, the feed mixture is heated by anexternal source of heat, such as by providing steam in returning gaspipes 85. The application of heat from the external source of heat maybe discontinued as soon as the total heat given off by the process andtransferred to the feed mixture, including the heat given off by thereformed gas mixture in the pipes, is sufficient to heat the feedmixture and the gas mixture in the interior chamber to a temperature ofabout 1100° F. at the output end of the kiln. The steam in theback-coming gas will condense in the pipes near the cool end of the kilnand give its heat of condensation to the warming of the incomingfeedstock within the kiln. The condenser completes the condensation.

The methanol reactor to go with a 300 ton/day gasifier might be 30 ft.long and 4 ft. in diameter, with an array of about 400 1" diameterheavy-walled pipes forming the rotor. It is akin, conceptually, to afire-tube boiler, with the synthesis gas-to-methanol exotherm providingthe heat to raise the steam.

The methanol reactor of the present invention is sturdy andstraightforward to build. Most of the components of the reactor can beconstructed from plate stock. For example, the spider plates-can besimple flat plate, bored for the gas pipes, with smaller holes in thespider plates between the pipes for water flow. The pipes can bespot-welded to the spider plates to give torque and sag resistance tothe rotor structure. The manifolds similarly will be constructed fromplate stock, with the shafts and pipes projecting through plates of themanifolds. As mentioned above, the pipes are bored between the plates ofthe manifold for gas entrance and egress and are plugged outside theplates for ease in cleaning. The pipes are welded to the outer surfaceof the plates of the manifold. The assembly is completed by welding ahoop around the perimeter of the plates.

Although illustrated and described herein with reference to certainspecific embodiments, the claims are not intended to be limited to thedetails shown. Rather, the claims should be read to include variousmodifications of the details shown without departing from the spirit ofthe invention.

What is claimed:
 1. A process for producing methanol from a feed gashaving hydrogen and carbon monoxide in an approximate 2:1 ratio, saidprocess comprising the steps of:(a) compressing and heating said feedgas; (b) introducing a heat transfer medium into an interior of aninclined vessel; (c) introducing the feed gas from step (a) into aplurality of conduits extending through the interior of said vessel,which conduits are in contact with said heat transfer medium and defineconduit flow paths isolated from said interior; (d) exposing said gas toa copper catalyst disposed in said conduit flow paths to cause thehydrogen and carbon monoxide to react to form methanol, while conductingsaid gas through said conduit flow paths to cause the temperature ofsaid gas to gradually drop, causing further formation of methanol fromthe hydrogen and carbon monoxide and causing the methanol to condense toa liquid.
 2. A process in accordance with claim 1 wherein:step (a) iscontinued until the pressure of said feed gas is from about 1400 psi to1600 psi and the temperature of said feed gas is from about 550° F. to650° F.; and step (d) is continued until the temperature of said gasdrops to a temperature of from about 70° F. to 130° F.
 3. A process inaccordance with claim 1 wherein:step (a) includes compressing said feedgas to about 1500 psi and heating said feed gas to about 600° F.; andstep (d) includes permitting the temperature of said gas and liquidmethanol mixture to gradually drop to about 100° F.
 4. A process inaccordance with claim 1 further comprising:placing a chain in each ofsaid plurality of conduits; placing said copper catalyst as pellets inthe links of said chain thereby exposing said gas to said coppercatalyst pellets as said gas is conducted through said conduits.
 5. Aprocess in accordance with claim 1 further comprising separatingunreacted feed gas from the methanol product.
 6. A process in accordancewith claim 5 further comprising filtering the methanol product to removeparticulates formed by catalyst shedding.
 7. A process in accordancewith claim 1 further comprising rotating said conduits within saidvessel.
 8. A process in accordance with claim 7 further comprisingrotating said conduits at a speed of about 1 to 2 rpm.
 9. A process forproducing methanol from a feed containing carbon, hydrogen and oxygen,said process comprising the steps of:(a) adding water and an alkalinecatalyst to the feed to form a feed mixture; (b) charging said feedmixture into an interior chamber of a rotor kiln at a first end of saidrotor kiln, which is tilted to permit gravity-driven travel in a firstdirection along said rotor kiln and which has a plurality of pipesextending along said rotor kiln in said first direction, wherein each ofsaid pipes defines a pipe flow path isolated from said interior chamber;(c) gradually heating said feed mixture to a temperature of from about1050° F. to 1150° F. to produce a gas mixture including CH₄, H₂, CO,CO₂, H₂ O, a trace amount of H₂ S, and about 1-2% condensable organiccompounds; (d) heating said gas mixture in a gas reformer while exposingsaid gas mixture to a nickel catalyst in said gas reformer to form areformed gas mixture having H₂ and CO in an approximate 2:1 ratio; (e)conducting said reformed gas mixture to said pipe flow paths at saidsecond end of said rotor kiln and permitting said reformed gas mixtureto flow through said pipes back to said first end of said pipes, whereinsaid reformed gas mixture in said pipes gives off the heat needed instep (c) to said feed mixture and said gas mixture in said interiorchamber to cool said reformed gas mixture to a temperature of about 300°F. to become a partially condensed mixture; (f) condensing saidpartially condensed mixture to form a condensed mixture; (g) removingimpurities including said trace amount of H₂ S from said condensedmixture and most of said CO₂ in an absorption vessel to form asubstantially pure mixture; (h) compressing and heating saidsubstantially pure mixture to a pressure of from about 1400 psi to 1600psi and a temperature of from about 550° F. to 650° F. to form a feedgas having hydrogen and carbon monoxide in an approximate 2:1 ratio; (i)introducing cool water into an interior of an inclined vessel; (j)introducing the feed gas into a plurality of conduits extending throughthe interior of said vessel, which conduits are in contact with saidcool water and define conduit flow paths isolated from said interior;(k) exposing said feed gas to a copper catalyst disposed in said conduitflow paths to cause the hydrogen and carbon monoxide to react to formmethanol, while conducting said feed gas through said conduit flow pathsto cause the temperature of said feed gas to gradually drop, causingfurther formation of methanol from the hydrogen and carbon monoxide andcausing the methanol to condense to a liquid; and (l) separatingunreacted feed gas from the methanol product.
 10. A process inaccordance with claim 9 further comprising:conducting a quantity of saidunreacted feed gas to said gas reformer and burning said quantity ofsaid unreacted feed gas at said gas reformer, wherein said quantity issufficient for heating said gas mixture in said gas reformer; andconducting a remaining quantity of said unreacted feed gas to saidinterior chamber of said rotor kiln at said first end of said rotorkiln.
 11. A process in accordance with claim 9 furthercomprising:conducting steam from said vessel, formed by the transfer ofheat from said feed gas, to a steam superheater atop said gas reformerto form superheated steam; conducting said superheated steam to aturbine generator to generate power; conducting the steam from saidturbine generator to said absorption vessel for transferring its heat ofcondensation to form water; and returning the water from said absorptionvessel to said vessel.
 12. A process in accordance with claim 9, whereinstep (c) is continued for about 30 to 90 minutes.
 13. A process inaccordance with claim 9 wherein step (c) includes initially heating saidfeed mixture with an external source of heat.
 14. A process inaccordance with claim 13, wherein step (c) further includesdiscontinuing the application of heat from said external source of heatas soon as the total heat given off by the process and transferred tosaid feed mixture, including the heat given off by said reformed gasmixture in said pipes, is sufficient to heat said feed mixture and saidgas mixture in said interior chamber to a temperature of about 1100° F.at said second end of said rotor kiln.